CN115304774B - Water-based epoxy curing agent with excellent performance and preparation method thereof - Google Patents
Water-based epoxy curing agent with excellent performance and preparation method thereof Download PDFInfo
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- CN115304774B CN115304774B CN202111114599.8A CN202111114599A CN115304774B CN 115304774 B CN115304774 B CN 115304774B CN 202111114599 A CN202111114599 A CN 202111114599A CN 115304774 B CN115304774 B CN 115304774B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 63
- 239000004593 Epoxy Substances 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 64
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 64
- 229920000768 polyamine Polymers 0.000 claims abstract description 40
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 35
- 229920000570 polyether Polymers 0.000 claims abstract description 35
- 229920005862 polyol Polymers 0.000 claims abstract description 35
- 150000003077 polyols Chemical class 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 22
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 17
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 17
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 229920002560 Polyethylene Glycol 3000 Polymers 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000004848 polyfunctional curative Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 238000010276 construction Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 abstract description 3
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006334 epoxy coating Polymers 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of C09D163/00, and particularly relates to an aqueous epoxy curing agent with excellent performance and a preparation method thereof. An aqueous epoxy curing agent with excellent performance is prepared from the following raw materials: epoxy resins, polyether polyols, polyamines. The active hydrogen of the waterborne epoxy curing agent prepared by the method is about 150g/Eq, the waterborne epoxy curing agent is used in combination with epoxy resin, the curing agent is less in dosage, the product performance is excellent, the cost is saved, and the application value of the product is improved; the aqueous epoxy resin curing agent prepared by the invention can be used for emulsifying liquid epoxy resin, such as E51 epoxy resin, and can be diluted by water instead of organic solvent in later construction, thereby being environment-friendly and economical.
Description
Technical Field
The invention belongs to the technical field of C09D163/00, and particularly relates to an aqueous epoxy curing agent with excellent performance and a preparation method thereof.
Background
The epoxy curing agent is an indispensable component in an epoxy coating system, and the epoxy coating is widely used in the fields of anti-corrosion coatings, metal primer, insulating paint and the like at present, however, the performance of the epoxy coating can be greatly improved by using the good epoxy curing agent.
However, conventional oily epoxy curing agents contain a large amount of organic solvents, such as the use of benzene-containing substances, which not only endanger the global ecological environment but also can be harmful to the physical health of humans. The development of the water-based epoxy curing agent at the present stage expands the application range for the use of the epoxy curing agent. The Chinese patent with the application number of 201911331062.X discloses a nonionic waterborne epoxy curing agent and a preparation method thereof, wherein the nonionic waterborne epoxy curing agent with controllable activity is prepared through the interaction between a polyepoxy compound and a polyamine compound and between a nonionic epoxy active emulsifier and a monoepoxy compound, but E51 epoxy resin or E44 epoxy resin with higher epoxy equivalent value is used in the published patent, the use amount and viscosity of the curing agent are greatly influenced, and the phenomenon of external dryness and internal wetness possibly occurs in the later construction process, so that the protection effect of metals is influenced.
For sustainable development of human beings, development of an aqueous epoxy curing agent with excellent performance in response to government environmental protection policies is an important research direction.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides an aqueous epoxy curing agent with excellent performance, which is prepared from the following raw materials: epoxy resins, polyether polyols, polyamines.
In some preferred embodiments, the epoxy resin is a bisphenol a type epoxy resin.
In some preferred embodiments, the bisphenol A type epoxy resin is selected from at least one of E-51, E-44, E-39, E-20.
Further preferably, the bisphenol A type epoxy resin is E-44 and E-20.
In some preferred embodiments, the weight ratio of E-44 to E-20 is 1: (0.1-10).
Further preferably, the weight ratio of E-44 to E-20 is 1:1.
the applicant found that the type and the addition amount of the selected epoxy resin have great influence on the performance of the prepared curing agent in the experimental process, and found through a great amount of creative experimental investigation by the applicant that in the application, the added epoxy resin is bisphenol A type epoxy resin, and the bisphenol A type epoxy resin uses E-44 and E-20, and the weight ratio of the bisphenol A type epoxy resin is ensured to be 1: (0.1-10), especially in the weight ratio of E-44 to E-20 of 1:1, the existence of the active hydrogen equivalent of about 150g/Eq can be ensured, the viscosity of the curing agent is ensured to be proper, the influence on construction is avoided in the use process of the curing agent at the later stage, and the phenomenon of external drying and internal wetting is caused.
In some preferred embodiments, the polyether polyol is selected from at least one of PEG400, PEG600, PEG800, PEG1000, PEG2000, PEG3000 polyether polyols.
In some preferred embodiments, the polyether polyol is PEG1000 and/or PEG2000.
The manufacturers of PEG1000 and PEG2000 are not particularly limited, and can purchase petrochemical engineering in sea-ampere in Jiangsu province.
In the experimental process, the applicant finds that the molecular weight of the polyether polyol has a great influence on the performance of the prepared curing agent, and when the PEG1000 and/or PEG2000 polyether polyol is used, the good adhesion effect of the polyether polyol on the surface of the substrate in the use process can be ensured, and the interaction strength between the polyether polyol and the substrate is improved.
In some preferred embodiments, the polyamine is selected from at least one of ethylenediamine, hydrazine hydrate, diethylenetriamine, triethylenetetramine, tetraethylenepentamine.
In some preferred embodiments, the polyamine is hydrazine hydrate and diethylenetriamine in a weight ratio of 1: (0.8-1.5).
Further preferably, the weight ratio of hydrazine hydrate to diethylenetriamine is 1:1.
through a great deal of experimental researches of the polyamine substances in the experimental process, the applicant finds that the interaction between the addition of the amine substances and the polyether polyol and the epoxy resin is enhanced, and particularly when the added polyamine substances are hydrazine hydrate and diethylenetriamine, the weight ratio of the added polyamine substances is 1: in the range of (0.8-1.5), the salt spray resistance of the prepared curing agent in the use process is greatly improved, and the applicant speculates that the reason for the phenomenon is as follows: through the interaction between the diethylenetriamine with the trifunctional degree and the hydrazine hydrate, the intermolecular interaction force is improved, the intermolecular interaction enhancement in the system is ensured, the formation of a protective film with higher compactness on the surface of a substrate is ensured, the excellent smoke resistance is further ensured when the metal surface is solidified, the service life is prolonged, and the application value is higher.
The second aspect of the invention provides a preparation method of an aqueous epoxy curing agent with excellent performance, which comprises the following steps:
1) Firstly, reacting polyether polyol with epoxy resin at the temperature of 80-150 ℃ to obtain modified epoxy resin;
2) And then reacting polyamine with the modified epoxy resin obtained in the step 1) at 70-90 ℃ to obtain polyamine substances, thus obtaining the water-based epoxy curing agent.
In some preferred embodiments, the temperature described in step 1) is 120 ℃.
The beneficial effects are that: the aqueous epoxy curing agent provided by the invention has the following advantages:
1. the waterborne epoxy curing agent prepared by the invention ensures that the active hydrogen equivalent of the waterborne epoxy curing agent is about 150g/Eq on the premise of the compound use of bisphenol A epoxy resin E-44 and E-20, can be matched with epoxy resin for use in the specific use process, especially E51 epoxy resin, can reduce the use amount of the curing agent, improves the adhesive force of the curing agent when the curing agent is used on the surface of a substrate, ensures the stability of a film layer, saves the cost and improves the application value of a product;
2. according to the water-based epoxy curing agent provided by the invention, under the condition that polyamine substances are used, especially under the condition that hydrazine hydrate and diethylenetriamine are compounded and used, the prepared curing agent can be ensured to have good salt spray resistance, the salt spray resistance test result shows that the salt spray resistance can be up to 700 hours, and in the salt spray resistance test of zinc-rich products, the result shows that the salt spray resistance can be up to 1200 hours, so that the application range of the curing agent is widened;
3. the aqueous epoxy resin curing agent prepared by the invention can emulsify liquid epoxy resin in the specific use process, for example, the aqueous epoxy resin curing agent is used together with E51 epoxy resin, water can be used for replacing organic solvent for dilution in later construction, the use of organic solvent is avoided, the environment-friendly requirement is compounded, water is used for replacing organic solvent, the subsequent recovery treatment process of organic solvent is reduced, the input cost is reduced, and the aqueous epoxy resin curing agent has higher economic benefit and economic value;
4. the water-based epoxy curing agent prepared by the method is researched through a large number of experiments, the preparation raw materials are easy to obtain, the preparation process is simple, and through the use of epoxy resin, polyether polyol and polyamine substances, the cost investment can be reduced to the greatest extent, the large-scale production can be realized, and the popularization value is higher.
Detailed Description
Examples
Example 1
The waterborne epoxy curing agent with excellent performance is prepared from the following raw materials in percentage by weight: 10% of epoxy resin, 40% of polyether polyol, 20% of polyamine and the balance of water to 100%.
The epoxy resin is E-44 and E-20, and the weight ratio is 1:1, purchasing from Guangzhou Kai green-gnonia chemical industry Co., ltd;
the polyether polyol is PEG1000, which is purchased from the petrochemical industry of sea-ampere in Jiangsu province;
the polyamine is hydrazine hydrate and diethylenetriamine.
The preparation method of the water-based epoxy curing agent with excellent performance comprises the following steps:
1) Firstly, reacting polyether polyol with epoxy resin at 120 ℃ to obtain modified epoxy resin;
2) And then reacting polyamine with the modified epoxy resin obtained in the step 1) at 80 ℃ to obtain polyamine substances, and finally adding water to react to obtain a finished product.
Example 2
The waterborne epoxy curing agent with excellent performance is prepared from the following raw materials in percentage by weight: 40% of epoxy resin, 10% of polyether polyol, 20% of polyamine and the balance of water to 100%.
The epoxy resin is E-44 and E-20, and the weight ratio is 1:1, purchasing from Guangzhou Kai green-gnonia chemical industry Co., ltd;
the polyether polyol is PEG1000, which is purchased from the petrochemical industry of sea-ampere in Jiangsu province;
the polyamine is hydrazine hydrate and diethylenetriamine, and the weight ratio of the hydrazine hydrate to the diethylenetriamine is 1:1.
the preparation method of the water-based epoxy curing agent with excellent performance comprises the following steps:
1) Firstly, reacting polyether polyol with epoxy resin at 120 ℃ to obtain modified epoxy resin;
2) And then reacting polyamine with the modified epoxy resin obtained in the step 1) at 80 ℃ to obtain polyamine substances, and finally adding water to react to obtain a finished product.
Example 3
The waterborne epoxy curing agent with excellent performance is prepared from the following raw materials in percentage by weight: 30% of epoxy resin, 10% of polyether polyol, 30% of polyamine and the balance of water to 100%.
The epoxy resin is E-44 and E-20, and the weight ratio is 1:1, purchasing from Guangzhou Kai green-gnonia chemical industry Co., ltd;
the polyether polyol is PEG1000, which is purchased from the petrochemical industry of sea-ampere in Jiangsu province;
the polyamine is hydrazine hydrate and diethylenetriamine, and the weight ratio of the hydrazine hydrate to the diethylenetriamine is 1:1.
the preparation method of the water-based epoxy curing agent with excellent performance comprises the following steps:
1) Firstly, reacting polyether polyol with epoxy resin at 120 ℃ to obtain modified epoxy resin;
2) And then reacting polyamine with the modified epoxy resin obtained in the step 1) at 80 ℃ to obtain polyamine substances, and finally adding water to react to obtain a finished product.
Example 4
The waterborne epoxy curing agent with excellent performance is prepared from the following raw materials in percentage by weight: 20% of epoxy resin, 20% of polyether polyol, 30% of polyamine and the balance of water to 100%.
The epoxy resin is E-44 and E-20, and the weight ratio is 1:1, purchasing from Guangzhou Kai green-gnonia chemical industry Co., ltd;
the polyether polyol is PEG1000, which is purchased from the petrochemical industry of sea-ampere in Jiangsu province;
the polyamine is hydrazine hydrate and diethylenetriamine, and the weight ratio is 1:1.
the preparation method of the water-based epoxy curing agent with excellent performance comprises the following steps:
1) Firstly, reacting polyether polyol with epoxy resin at 120 ℃ to obtain modified epoxy resin;
2) And then reacting polyamine with the modified epoxy resin obtained in the step 1) at 80 ℃ to obtain polyamine substances, and finally adding water to react to obtain a finished product.
Example 5
The waterborne epoxy curing agent with excellent performance is prepared from the following raw materials in percentage by weight: 30% of epoxy resin, 20% of polyether polyol, 30% of polyamine and the balance of water to 100%.
The epoxy resin is E-51, and is purchased from Guangzhou Kai green-gnonia chemical industry Co., ltd;
the polyether polyol is PEG1000, which is purchased from the petrochemical industry of sea-ampere in Jiangsu province;
the polyamine is hydrazine hydrate and diethylenetriamine, and the weight ratio is 1:1.
the preparation method of the water-based epoxy curing agent with excellent performance comprises the following steps:
1) Firstly, reacting polyether polyol with epoxy resin at 120 ℃ to obtain modified epoxy resin;
2) And then reacting polyamine with the modified epoxy resin obtained in the step 1) at 80 ℃ to obtain polyamine substances, and finally adding water to react to obtain a finished product.
Example 6
The waterborne epoxy curing agent with excellent performance is prepared from the following raw materials in percentage by weight: 30% of epoxy resin, 15% of polyether polyol, 30% of polyamine and the balance of water to 100%.
The epoxy resin is E-44, and is purchased from Guangzhou Kai green-gnonia chemical industry Co., ltd;
the polyether polyol is PEG1000, which is purchased from the petrochemical industry of sea-ampere in Jiangsu province;
the polyamine is hydrazine hydrate and diethylenetriamine, and the weight ratio is 1:1.
the preparation method of the water-based epoxy curing agent with excellent performance comprises the following steps:
1) Firstly, reacting polyether polyol with epoxy resin at 120 ℃ to obtain modified epoxy resin;
2) And then reacting polyamine with the modified epoxy resin obtained in the step 1) at 80 ℃ to obtain polyamine substances, and finally adding water to react to obtain a finished product.
Example 7
An aqueous epoxy curing agent with excellent performance, the specific implementation mode of the aqueous epoxy curing agent is the same as that of example 4, and the weight ratio of hydrazine hydrate to diethylenetriamine is 1:2.
performance test:
1. salt spray resistance test: the curing agents prepared in examples 1 to 7 were used for salt spray resistance test, the test method was referred to GB/T1771-1991, the test substrates were divided into copper plates and zinc-rich plates, and the test results were recorded in the following table.
2. Adhesion test: the curatives prepared in examples 1-7 were used for adhesion testing with reference to GB/T9286-88 and the test results are recorded in the following table.
3. Impact resistance test: the curing agent prepared in examples 1-7 was used for impact resistance testing, the test method was referred to GB/T1732-93, the impact resistance testing was performed on both the side coated with the curing agent and the back side coated with the curing agent, the standard judgment was that 1kg of weight was free to fall at 50cm high altitude, the surface of the curing agent was judged to be damaged, and if there was no change, pass was made; no is the case when the surface is damaged.
The product obtained by the invention is matched with liquid epoxy resin (such as E51 epoxy resin) or modified epoxy resin EL-2075 (Yixing China chemical materials Co., ltd.) for use, has long use window period, higher paint film drying speed and excellent paint film comprehensive performance, and is widely used for preparing high-solid-content water-based epoxy paint for metal protection.
Claims (5)
1. The waterborne epoxy curing agent with excellent performance is characterized in that the preparation raw materials are as follows: epoxy resins, polyether polyols, polyamines;
the epoxy resin is bisphenol A epoxy resin, the bisphenol A epoxy resin is E-44 and E-20, and the weight ratio of the E-44 to the E-20 is 1: (0.1-10);
the polyamine is hydrazine hydrate and diethylenetriamine, and the weight ratio of the hydrazine hydrate to the diethylenetriamine is 1: (0.8-1.5).
2. The excellent waterborne epoxy curing agent according to claim 1, wherein the polyether polyol is at least one selected from the group consisting of PEG400, PEG600, PEG800, PEG1000, PEG2000 and PEG3000 polyether polyols.
3. The excellent waterborne epoxy curing agent according to claim 1, wherein the polyether polyol is PEG1000 and/or PEG2000.
4. A method for producing the excellent-performance aqueous epoxy curing agent according to any one of claims 1 to 3, characterized by comprising the steps of:
1) Firstly, reacting polyether polyol with epoxy resin at the temperature of 80-150 ℃ to obtain modified epoxy resin;
2) And then reacting polyamine with the modified epoxy resin obtained in the step 1) at 70-90 ℃ to obtain polyamine substances, thus obtaining the water-based epoxy curing agent.
5. The method for producing an aqueous epoxy hardener excellent in properties according to claim 4, wherein the temperature in step 1) is 120 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563927A (en) * | 2019-10-10 | 2019-12-13 | 杭州崇成科技有限公司 | Water-based epoxy resin curing agent and preparation method thereof |
| CN110684178A (en) * | 2019-09-11 | 2020-01-14 | 中国石油大学(华东) | Preparation and application method of nonionic waterborne epoxy curing agent |
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| CN110684178A (en) * | 2019-09-11 | 2020-01-14 | 中国石油大学(华东) | Preparation and application method of nonionic waterborne epoxy curing agent |
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